scholarly journals The absorption spectra of halogens and inter-halogen compounds in solution in carbon tetrachloride

When two solutions are mixed the absorption spectrum of the new solution will be the mean of those of the separate solutions provided that no chemical interaction occures. The mere fact of a departure from additivity does not, however, necessarily denote the formation of true chemical compounds. The solute or solutes may undergo solvation, loosely bound aggregates may occur, and even when marked deviations from the simple law of mixtures are observed it is rarely possible to prove the quantitative formation of a given chemical compound from spectroscopic data alone. The above considerations apply with some force to the problem of the absorption spectra of halogens and inter-halogen compounds in an inert solvent. The three elements show perfectly characteristic absorption bands, they are known to interact with the formation of some quite stable compounds, some relatively stable compounds, and some apparently very unstable compounds.

Butadiene is important as the simplest example of resonance between two conjugated double bonds. The comparison of its ultra-violet absorption spectrum with that of ethylene might be expected to give some indication of the way the π electrons of the molecule are affected by the resonance. The electronic structures of a number of molecules for which resonance is important have been worked out theoretically by Hückel (1935), Lennard- Jones (1937), Sklar (1937) and Mulliken (1939 a and b ). The purpose of the present work is to obtain spectroscopic data with which the theoretical expectations can be compared. As most of the strong absorption bands of these molecules occur at wave-lengths less than 2000 A, the investigation falls naturally into the region of vacuum spectroscopy.


In 1874 it was shown by Roscoe and Schuster that channelled absorption spectra can be obtained with the vapours of the alkali elements sodium and potassium, and later on these spectra were investigated in some detail by Liveing and Dewar. It was also shown in 1896 by Weidemann and Schmidt that the vapours of these same metals emitted a radiation possessing characteristics of a fluorescence spectrum when they were traversed by white light. Since 1903 exhaustive studies have been made of both the fluorescence and the channelled absorption spectrum of sodium by R. W. Wood, together with a number of collaborators, Including J. H. Moore and F. E. Hackett. In these investigation it was shown that the channelled absorption spectrum of sodium was made up of a number of series of absorption bands, one set of series being on the red wave-length side of the D lines, and another lying in the visible blue-green region. In addition, series of absorption bands were found by them with approximately regular spacing in the neighbourhood of λ = 3303 A, the second member of the doublet series of this element. As regards the fluorescence spectrum of sodium, they found that, by stimulation of the vapour with approximately monochromatic light, there resulted an emission of light, the spectrum of which consisted of a number of bright but narrow bands of varying intensity, more or less regularly spaced both above and below the mean wave-length of the exciting light. They observed, too, that the slightest change in the wave-length of the exciting light resulted in the disappearance of one set of lines and in the appearance of another of different wave-lengths. In the various florescence spectra obtained by R. W. Wood when stimulating sodium vapour by monochromatic light from different sources, it was noted that there was a remarkable recurrence of the interval, ∆ λ = 52·3 A. in the spacing of the fluorescence bands.


2002 ◽  
Vol 56 (1) ◽  
pp. 24-30 ◽  
Author(s):  
Marta KlanjšEk Gunde ◽  
Zorica Crnjak Orel

Thickness-dependent intensities and positions of absorption lines in infrared reflection-absorption spectra of thin films on reflective substrates at near-normal incidence are investigated. Two types of absorption bands in a polymer, the weak and the strong, were examined. Their optical properties were determined by the dielectric response function. The optical path of the beam was described by the coherent sum of all successively reflected beams. The thickness-dependent properties of absorption bands were examined in three typical thickness regions. At small thickness, the peak intensity oscillates around the mean value defined by the simple internal absorptance of the beam crossing the double layer. For medium thickness, the peak position swings around the original frequency and its intensity oscillations move above the simple internal absorptance. In layers within the high-thickness region, optical distortions cause large changes in line shape due to approaching the bulk reflectance. A simple analytical interpretation is possible only within the low-thickness region. The width of these thickness regions depends on the absorptivity of the considered band; for strong bands they are considerably narrower than for weak bands. The theoretically predicted effects compare well with those measured in RAS spectra of variously thick silicon resin layers on aluminium substrates.


1981 ◽  
Vol 59 (12) ◽  
pp. 1908-1916 ◽  
Author(s):  
M. Barnett ◽  
E. A. Cohen ◽  
D. A. Ramsay

Absorption spectra of isotopically enriched 81Br16O and of normal BrO have been obtained by the flash photolysis of mixtures of bromine and ozonized oxygen. Rotational analyses are given for the 7–0, 12–0, 18–0, 19–0, 20–0, 21–0, 7–1, and 20–1 A2Π3/2–X2Π3/2 sub-bands of 81Br16O. The value for [Formula: see text] is found to be 722.1 ± 1.1 cm−1 in good agreement with the value calculated from microwave constants. Several additional bands have been found at the long wavelength end of the spectrum, necessitating a revision of the vibrational numbering scheme for both the emission and absorption bands. "Hot" bands up to ν″ = 6 have been observed in the absorption spectrum for the 2Π3/2 component of the ground state but no bands have yet been identified from the 2Π1/2 component.


2009 ◽  
Vol 5 (S263) ◽  
pp. 237-239
Author(s):  
Anderson O. Ribeiro ◽  
Fernando Roig

AbstractIn this work, we propose to analyse the existence of possible correlations between the taxonomic classes of asteroids showing featureless spectra –i.e. a flat continuum with no absorption bands– and their orbital properties. We compute the mean spectral slope of 14 753 asteroids using the photometric data from the Sloan Digital Sky survey Moving Objects Catalog (SDSS-MOC4). Although the quality of these data is not comparable in resolution to the spectroscopic data, the amount of observations in the SDSS-MOC4 is more than 20 times larger that in the available spectral databases. This allows us to obtain a statistically significant result.


1995 ◽  
Vol 50 (4) ◽  
pp. 551-557 ◽  
Author(s):  
Kenta Takahashi ◽  
Keisuke Umakoshi ◽  
Akihiro Kikuchi ◽  
Yoichi Sasaki ◽  
Masato Tominaga ◽  
...  

New trinuclear rhodium(III) complexes, [Rh3(μ3-O)(μ-CH3COO)6(L)3]+ (L = imidazole (Him), 1-methylimidazole (Meim), and 4-methylpyridine (Mepy)) have been prepared. The Him, Meim, and Mepy complexes show reversible one-electron oxidation waves at E1/2 = +1.12, +1.12, and +1.28 V vs Ag/AgCl, respectively, in acetonitrile. Electronic absorption spectra of the one electron oxidized species of these complexes and [Rh3(μ3-O)(μ-CH3COO)6(py)3]+ (py = pyridine) (E1/2 = +1.32 V ) were obtained by spectroelectrochemical techniques. While the Rh3(III,III,III) states show no strong visible absorption, the Rh3(III,III,IV ) species give a band at ca. 700 nm (ε = 3390-5540 mol dm-3 cm-1). [Ir3(μ3-O)(μ-CH3COO)6(py)3]+ with no strong absorption in the visible region, shows two reversible one-electron oxidation waves at +0.68 and +1.86 V in acetonitrile. The electronic absorption spectrum of the one-electron oxidized species (Ir3(III,III,IV )) also shows some absorption bands (688 nm (ε, 5119), 1093 (2325) and 1400 (ca. 1800)). It is suggested that the oxidation removes an electron from the fully occupied anti-bonding orbital based on metal-dπ-μ3-O-pπ interactions, the absorption bands of the (III,III,IV ) species being assigned to transitions to the anti-bonding orbital.


Clay Minerals ◽  
1984 ◽  
Vol 19 (1) ◽  
pp. 107-111 ◽  
Author(s):  
A. Julg ◽  
O. Julg

The spectrum of Ni-substituted lizardite, (Mg,Ni)3Si2O5(OH)4, has been discussed by many authors, who have successively given contradictory interpretations concerning the symmetry of the Ni-sites. Lakshman & Reddy (1973) affirmed that in garnierites Ni is in a tetrahedral site. Faye (1974) rejected this conclusion and showed that Ni2+ occupies an octahedral site. However, the Ni … O distance of 2·01 Å which he deduced from the intensity of the crystal field is unacceptable. Recently, using a completely different approach to the interpretation of the spectrum, Cervelle & Maquet (1982) claimed that Ni2+ occupies a six-coordinated site of C3v symmetry, and concluded that the mean Ni … O distance is 2·06 Å.The aim of this note is to show that it is possible to interpret the spectrum of Ni-lizardite as arising from a predominantly octahedral field with a weak C2v component which provokes a small increase in width of the absorption bands.


1877 ◽  
Vol 25 (171-178) ◽  
pp. 4-4

The paper contains the results of an exact series of measurements of the absorption-spectra of the vapours of the element bromine and of the compound iodine monochloride, made with the object of ascertaining whether the molecules of these two gases vibrate identically or similarly, their molecular weights and colour of the vapours being almost identical. The two spectra, which are both channelled, were compared simultaneously by means of one of Kirchhoff’s 4-prism spectroscopes, the position of the lines being read off by reflection on an arbitrary scale. In order to determine the wave-lengths of these bands, the wave-length of each of 27 air-lines lying between the extremes of the absorption-spectra was ascertained by reference to Thalén’s numbers; whilst for the purpose of reducing the readings of the absorption-bands to wave-lengths a graphical method was employed, the details of which are given in the paper. This method appears to be one of general applicability for the plotting of spectra. Tables then follow giving the wave-lengths of 66 bands of each absorption-spectrum; and a map accompanies the text in which the bands are drawn to a scale one half that of Ångström’s “Spectre Normal.”


1949 ◽  
Vol 27b (11) ◽  
pp. 828-860 ◽  
Author(s):  
R. Norman Jones ◽  
G. Denis Thorn

The ultraviolet absorption bands associated with the following groups have been investigated in a variety of compounds of known structure:[Formula: see text]The groups may be characterized by the ultraviolet spectrum, and the number of each type of group present in a given compound may be estimated from an analysis of the shape and intensity of the absorption spectrum. These correlations have been applied to the elucidation of the structure of new compounds isolated in the course of the investigation of the chemistry of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX).


1960 ◽  
Vol 13 (2) ◽  
pp. 222 ◽  
Author(s):  
GJ Sutton

A study has been made of the bis(2-picolylamine) copper(II) complex in association with various anions. Of the salts investigated, the chloride bromide, and nitrate are blue, the iodide is green, and the perchlorate and tetraiodomercurate are purple. Blue solutions are obtained in water, and the molecular absorption spectra are identical and are characteristic of bispicolylamine copper(II) ion. However, conductance measurements in methanol and nitromethane show that there is some metal halogen bonding for the iodide, and this is also indicated by a slight shift in the absorption spectrum to longer wavelengths in the same solvents. The mean magnetic moment of the copper atom in the complexes was found to be 1.93 B.M.


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